The oxidation of peroxide by disordered metal oxide water oxidation catalysts: a measurement of thermodynamic stability "by proxy"

Sabri, Mayada, King, Hannah J., Gummow, Rosalind J., Malherbe, Francois, and Hocking, Rosalie K. (2018) The oxidation of peroxide by disordered metal oxide water oxidation catalysts: a measurement of thermodynamic stability "by proxy". ChemPlusChem, 83 (7). pp. 620-629.

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Abstract

It is often noted that disordered materials have different chemical properties to their more "ordered" cousins. Quantifying these effects in terms of thermodynamics is challenging in part because disordered materials can be difficult to characterise and are frequently relatively unstable. During the course of our experiments to understand the effects of disorder in catalysts for water oxidation we observed that many disordered manganese and cobalt oxide water oxidation catalysts directly oxidised peroxide in contrast to their more ordered analogues which catalysed its disproportionation i.e. MnO2 + 2H+ + H2O2 → Mn2+ + 2H2O + O2 (oxidation reaction) versus H2O2→ H2O + ½O2 (disproportionation reaction). By measuring the efficiency for one reaction over the other as a function of pH, we were able to quantify the relative stability of materials in two metal oxide series and thereby quantify their relative thermodynamic stability, "by proxy". We found that for the series of catalysts investigated the disorder made the materials stronger chemical oxidants and worse catalysts for the disproportionation of peroxide.

Item ID: 18968
Item Type: Article (Research - C1)
ISSN: 2192-6506
Funders: Swinburne University (SU), James Cook University, Ministry of Higher Education, Iraq, Australian Government
Projects and Grants: SU Vice Chancellor's Women in STEM fellowship
Date Deposited: 28 Jun 2018 05:37
FoR Codes: 03 CHEMICAL SCIENCES > 0306 Physical Chemistry (incl Structural) > 030601 Catalysis and Mechanisms of Reactions @ 70%
03 CHEMICAL SCIENCES > 0302 Inorganic Chemistry > 030207 Transition Metal Chemistry @ 0%
03 CHEMICAL SCIENCES > 0306 Physical Chemistry (incl Structural) > 030605 Solution Chemistry @ 30%
SEO Codes: 85 ENERGY > 8599 Other Energy > 859999 Energy not elsewhere classified @ 20%
97 EXPANDING KNOWLEDGE > 970103 Expanding Knowledge in the Chemical Sciences @ 80%
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